CN115485256A - Process for producing monofluoromethane - Google Patents
Process for producing monofluoromethane Download PDFInfo
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- CN115485256A CN115485256A CN202180031838.5A CN202180031838A CN115485256A CN 115485256 A CN115485256 A CN 115485256A CN 202180031838 A CN202180031838 A CN 202180031838A CN 115485256 A CN115485256 A CN 115485256A
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- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 64
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 50
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 50
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 49
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011737 fluorine Substances 0.000 claims abstract description 48
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- 125000000962 organic group Chemical group 0.000 claims abstract description 11
- 238000007599 discharging Methods 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims description 17
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 abstract description 8
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 51
- 239000012071 phase Substances 0.000 description 15
- 230000008016 vaporization Effects 0.000 description 13
- 238000009834 vaporization Methods 0.000 description 12
- 239000013076 target substance Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- -1 formyloxy Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical class [O-][N+](*)=O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/357—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by dehydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a method for producing monofluoromethane by a gas phase flow method without using a catalyst. The present invention is a method for producing monofluoromethane, comprising the steps of discharging a raw material gas containing a fluorine-containing inorganic compound and a fluorine-containing inorganic compound in a continuously circulating state, and then continuously discharging the raw material gas outside the discharge region, wherein the raw material gas is represented by formula 1: CH (CH) 3 -R [ wherein R is a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom or an organic group (except for a hydrocarbon group).]The compounds shown, and non-reactive gases.
Description
Technical Field
The present invention relates to a method for producing monofluoromethane.
Background
Monofluoromethane is widely used for applications such as etching gases for microfabrication of semiconductors.
Further, as a method for producing monofluoromethane, the following methods are known: reacting methyl Chloride (CH) in the presence of a fluorination catalyst 3 Cl) with hydrogen fluoride in a gas phase to obtain a mixed gas containing monofluoromethane, and then separating and purifying monofluoromethane from the mixed gas.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2006-111611.
Disclosure of Invention
Problems to be solved by the invention
However, the above-mentioned method for producing monofluoromethane not only imposes a large burden on the production of the fluorination catalyst, but also causes a decrease in yield with a decrease in the activity of the catalyst, and thus continuous production is difficult.
Accordingly, an object of the present invention is to provide a production method capable of producing monofluoromethane in a vapor-phase flow manner without using a catalyst.
The present inventors have conducted extensive studies to achieve the above object, and as a result, have found that monofluoromethane can be obtained by discharging a raw material gas in a continuously flowing state and then continuously discharging the raw material gas outside the discharge region, and have completed the present invention.
The present invention is directed to advantageously solve the above problems, and the present invention relates to a method for producing monofluoromethane, comprising the steps of discharging a raw material gas containing a fluorine-containing inorganic compound, formula 1: CH (CH) 3 R [ wherein R is a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom or an organic group (except for the hydrocarbon group) ]]The compounds shown and an inert gas.
Hereinafter, monofluoromethane is also referred to as "target substance".
The "inorganic compound" in the "fluorine-containing inorganic compound" refers to a compound containing no carbon atom and a compound containing one carbon atom and containing no hydrogen atom.
In the method for producing monofluoromethane according to the present invention, a raw material gas is discharged in a state of being continuously circulated, the raw material gas is converted into a reaction gas containing radicals which are precursors of monofluoromethane, and then the reaction gas is continuously discharged outside the discharge region, thereby producing monofluoromethane. As described above, according to the present invention, monofluoromethane can be produced in a gas phase flow system without using a catalyst.
In the process for producing monofluoromethane of the present invention, the fluorine-containing inorganic compound is preferably selected from SF 4 、SF 6 、SOF 2 、SO 2 F 2 、HF、NF 3 、CF 4 、BF 3 And SiF 4 More than one of them. These fluorine-containing inorganic compounds can easily generate active species of fluoromonomers upon discharge.
In the method for producing monofluoromethane according to the present invention, the inert gas may be selected from N 2 And Ar.
Further, in the method for producing monofluoromethane according to the present invention, it is preferable that the total content ratio of the fluorine-containing inorganic compound and the compound represented by the formula 1 in the raw material gas is 1 vol% or more and 85 vol% or less. When the total content ratio of the fluorine-containing inorganic compound and the compound of formula 1 is within the above range, monofluoromethane, which is a target substance, can be efficiently produced.
In the method for producing monofluoromethane according to the present invention, the volume ratio of the fluorine-containing inorganic compound to the compound represented by formula 1 is preferably 0.8 or more. If the volume ratio of the fluorine-containing inorganic compound to the compound of formula 1 is not less than the above lower limit, the by-production of hydrocarbons can be sufficiently suppressed.
Further, in the method for producing monofluoromethane according to the present invention, the volume ratio of the fluorine-containing inorganic compound to the compound represented by the formula 1 is preferably 1.8 or more.
Effects of the invention
According to the present invention, monofluoromethane can be produced in a gas phase flow manner without using a catalyst. The production method of the present invention can avoid a decrease in yield due to a decrease in activity of the catalyst, and can continuously produce monofluoromethane.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
[ fluorine-containing inorganic Compound ]
The fluorine-containing inorganic compound may be any inorganic compound containing at least one fluorine atom, and usually the number of fluorine atoms is 8 or less.
Examples of the fluorine-containing inorganic compound include SF 4 、SF 6 、SOF 2 、SO 2 F 2 、HF、NF 3 、CF 4 、BF 3 、SiF 4 And the like. From the viewpoint of ease of handling, SF is preferred 6 、NF 3 、CF 4 More preferably SF 6 . These may be used alone, or two or more kinds may be used in combination at an arbitrary ratio.
[ Compound of formula 1]
The compound of formula 1 is formula 1: CH (CH) 3 -R [ wherein R is a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom or an organic group (except for a hydrocarbon group).]The compound shown in the specification. The compound of formula 1 may be used alone, or two or more compounds may be used in combination at an arbitrary ratio.
In the present specification, the organic group (excluding the hydrocarbon group) means a functional group containing at least one carbon atom (excluding a functional group consisting of only carbon atoms and hydrogen atoms) and a functional group containing at least one selected from oxygen, nitrogen and sulfur and not containing a carbon atom, and examples thereof include an oxygen-containing organic group, a nitrogen-containing organic group and a sulfur-containing organic group.
As the oxygen-containing organic group, there may be mentioned, examples thereof include a hydroxyl group (-OH), a carboxyl group (-COOH), a formyl group (-CHO), and formyloxy (- = O), acyl (-CR) 1 (= O)), acyloxy group (-O-CR) 1 (= O)), alkoxy group (-OR) 1 ) Alkoxycarbonyl group (- = O) -OR 1 ) And the like. Wherein R is 1 The alkyl group is preferably a C1-C4 alkyl group, and more preferably a methyl group or an ethyl group.
As containing nitrogen withAs the organic group, there may be mentioned unsubstituted amino (-NH) 2 ) Substituted amino group (-NR) 2 R 3 ) Nitro (-NO) 2 ) Cyano (-CN), and the like. Wherein R is 2 And R 3 Independently hydrogen or alkyl, but at least one is alkyl, preferably C1-C4 alkyl, more preferably methyl or ethyl.
Examples of the sulfur-containing organic group include a mercapto group (-SH), and a sulfonic acid group (-SO) 3 H) Alkylthio (-SR) 4 ) And the like. Wherein R is 4 The alkyl group is preferably a C1-C4 alkyl group, and more preferably a methyl group.
R is preferably a hydrogen atom, chlorine atom, bromine atom, iodine atom, hydroxyl group (-OH), alkoxy group (-OR) 1 ) Acyl group (-CR) 1 (= O)), substituted amino group (-NR) 2 R 3 ) (wherein, R 1 、R 2 And R 3 As described above. ) More preferred are a hydrogen atom, a chlorine atom, a hydroxyl group, a methoxy group, an acetyl group and a dimethylamino group.
As the compound of formula 1, CH may be mentioned 4 、CH 3 OH、CH 3 Cl、CH 3 Br、CH 3 I、CH 3 CHO、HCOOCH 3 、CH 3 COOCH 3 、CH 3 COOC 2 H 5 、CH 3 NH 2 、(CH 3 ) 2 NH、(CH 3 ) 3 N、CH 3 CN、CH 3 NO 2 、CH 3 SH、CH 3 SCH 3 、CH 3 OCH 3 、CH 3 OC 2 H 5 、CH 3 COCH 3 、CH 3 COC 2 H 5 Etc., preferably CH from the viewpoint of ease of handling 4 、CH 3 OH、CH 3 Cl、CH 3 COCH 3 、CH 3 OCH 3 、(CH 3 ) 3 N, more preferably CH 3 OH。
[ inert gas ]
As the inert gas, N is mentioned 2 、He、Ne、Ar、Xe、Kr、CO、CO 2 Etc., preferably N 2 、Ar、He、CO、CO 2 More preferably N 2 And Ar. Non-reactive gasOnly one kind may be used, or two or more kinds may be used in combination at an arbitrary ratio.
[ raw gas ]
The raw material gas contains a fluorine-containing inorganic compound, a compound of formula 1, and an inert gas. The fluorine-containing inorganic compound and the compound of formula 1 may be any of a gas, a liquid, and a solid in a standard state (atmospheric pressure, 25 ℃), but are a gas when a raw material gas is discharged. The remaining portion of the raw material gas other than the fluorine-containing inorganic compound, the compound of formula 1, and the inert gas is preferably an impurity that inevitably mixes in from the ambient environment.
The content ratio of the fluorine-containing inorganic compound, the compound of formula 1, and the inert gas in the raw material gas is not particularly limited, and can be adjusted at an arbitrary ratio. The total content ratio of the compound of formula 1 and the fluorine-containing inorganic compound in the raw material gas is preferably 0.1% by volume or more, more preferably 0.5% by volume or more, and still more preferably 1% by volume or more, and is preferably 95% by volume or less, more preferably 90% by volume or less, and still more preferably 85% by volume or less. In this case, the remaining part of the raw material gas is preferably an inert gas and impurities inevitably mixed in from the ambient environment.
The volume ratio of the fluorine-containing inorganic compound to the compound of formula 1 in the raw material gas is not particularly limited, and can be adjusted at an arbitrary ratio. The volume ratio of the fluorine-containing inorganic compound to the compound of formula 1 is preferably 0.8 or more from the viewpoint of suppressing the by-production of hydrocarbons, and more preferably 1.8 or more from the viewpoint of producing the target substance. The volume ratio of the fluorine-containing inorganic compound to the compound of formula 1 may be 100 or less, and for example, 25 or less.
The raw material gas may contain a fluorine-containing inorganic compound, a compound of formula 1, and an inert gas at the time of discharge. For example, in order to discharge, the compound of formula 1, the fluorine-containing inorganic compound, and the inert gas may be supplied individually in a gaseous state as raw material gases, or all of them may be supplied as raw material gases as premixed gases, or a part of them may be supplied as premixed gases and supplied separately from the rest of the gases as raw material gases, in a gas phase flow reactor having a discharge mechanism (hereinafter, also simply referred to as "gas phase flow reactor").
In the case where the compound of formula 1 or the fluorine-containing inorganic compound is a gas in a standard state or a liquid having a sufficiently high vapor pressure and being easily vaporized by heating or the like, the compound of formula 1 or the fluorine-containing inorganic compound can be supplied in a gaseous state to the gas phase flow reactor without providing a separate vaporization chamber or the like. The supply flow rate can be controlled by using a mass flow controller or the like.
In the case where the compound of formula 1 or the fluorine-containing inorganic compound is a liquid or a solid having a low vapor pressure in a standard state, the compound of formula 1 or the fluorine-containing inorganic compound may be supplied to a gas-phase flow reactor after being gasified in a separate gasification chamber. In the case of a solid, the solid can be heated to become a liquid, and then introduced into the vaporization chamber.
For example, the compound of formula 1 or the fluorine-containing inorganic compound can be vaporized by introducing the compound of formula 1 or the fluorine-containing inorganic compound in a liquid state into a vaporization chamber maintained at a temperature and pressure at which the compound of formula 1 or the fluorine-containing inorganic compound is sufficiently vaporized. The temperature and pressure of the gasification chamber are preferably maintained at a temperature and pressure at which the compound of formula 1 or the fluorine-containing inorganic compound can be instantaneously gasified. By using such a vaporization chamber, the compound of formula 1 or the fluorine-containing inorganic compound can be continuously introduced into the vaporization chamber in a liquid state, instantaneously vaporized in the vaporization chamber, and continuously supplied to the gas-phase flow reactor in a gaseous state. The control of the supply flow rate can be performed by controlling the gas vaporized in the vaporization chamber by using a mass flow controller or the like, or by using a compound of formula 1 or a fluorine-containing inorganic compound of formula 1 such as a liquid mass flow controller or the like when the compound or the fluorine-containing inorganic compound is continuously introduced into the vaporization chamber in a liquid state. In the case of vaporizing both the compound of formula 1 and the fluorine-containing inorganic compound, both may be vaporized in different vaporization chambers, or both may be vaporized in the same vaporization chamber, but from the viewpoint of setting of vaporization conditions and control of supply flow rate, it is preferable to vaporize both in different vaporization chambers. When the vaporized compound of formula 1 and the fluorine-containing inorganic compound are introduced into the gas phase flow reactor, they may be diluted with an inert gas.
The space velocity when the raw material gas is continuously circulated in the gas-phase flow reactor is not particularly limited, but is preferably 0.01h -1 Above, more preferably 0.1h -1 Above, more preferably 0.3h -1 Above, and preferably 100000h -1 Hereinafter, 50000h is more preferable -1 Hereinafter, 10000h is more preferable -1 The following. If the space velocity is within the above range, difficulty in discharge can be avoided, and the target substance can be efficiently produced without lowering productivity.
[ discharge ]
By discharging the raw material gas in the gas-phase flow reactor, various active species can be generated from the fluorine-containing inorganic compound contained in the raw material gas and the compound of formula 1. The compounds of formula 1 are particularly prone to generate CH as a precursor to monofluoromethane upon discharge 3 Free radicals are advantageous.
As a method of discharging the raw material gas, a method having an electrode to which a voltage for causing discharge is applied can be used, and for example, a method such as high-frequency discharge, microwave discharge, dielectric barrier discharge, glow discharge, arc discharge, corona discharge, or the like can be used. From the viewpoint of stability of discharge and throughput of gas, high-frequency discharge, glow discharge, and arc discharge are preferable.
In the discharge method used, the pressure (absolute pressure) at the time of discharge is not particularly limited as long as the raw material gas can be discharged, and is preferably 1pa or more, more preferably 5pa or more, and preferably 1mpa or less, more preferably 0.5mpa or less. If the pressure (absolute pressure) is within the above range, the target substance can be efficiently produced.
[ target substance ]
By continuously discharging the material gas after the discharge from the discharge region, the generated active species are recombined to generate monofluoromethane as a target substance. The continuous discharge can be performed at a space velocity corresponding to the continuous flow of the raw material gas.
Here, the discharge region refers to a space in which discharge of the source gas is caused. For example, in the case of a gas phase flow reactor having parallel flat plate electrodes as a discharge mechanism, the discharge region refers to a space in which discharge occurs between the electrodes. The discharge to the outside of the discharge region means discharge from the inside of the space to the outside.
The gas after discharge may be discharged to the outside of the discharge region and discharged from the gas-phase flow reactor, and then introduced into a heat exchanger to be cooled. The heat exchanger is not particularly limited in form, and examples thereof include an air-cooling type and a water-cooling type. Since the effluent contains hydrocarbons and the like in addition to the target substance, the target substance can be separated and purified by a separation and purification step that can be optionally performed. Examples of the separation and purification method include distillation, absorption by a solution or the like, membrane separation, and the like.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
(example 1)
Using CH 3 OH (vapor) as Compound of formula 1, SF 6 As the fluorine-containing inorganic compound and Ar as an inert gas, 10sccm, 5sccm and 285sccm of each gas phase flow reaction tube made of metal and having a parallel flat plate electrode capable of high-frequency discharge installed therein were introduced (frequency 60MHz, capacity 35L).
A mixed gas of the compound of formula 1, a fluorine-containing inorganic compound and an inert gas was discharged in a reaction tube with a supply power of 500W while maintaining a pressure of 10PaA (absolute pressure). The gas was continuously discharged from the reaction tube and collected with an aluminum bag. A neutralization pipe filled with KOH particles is provided in front of the aluminum bag, and the collected gas is the gas that has passed through the neutralization pipe.
The collected gas was separated by a mass spectrometer gas chromatograph (GC-MS) (Agilent 7890A manufactured by Agilent) and a hydrogen flame ionization gas chromatograph (GC-FID) (Agilent 6890N manufactured by Agilent)And (4) performing analysis. From the analyzed area values of the components GC-FID and GC-MS, the molar conversion of the compound of formula 1 was determined as the conversion of the starting material. Further, CH in the product is determined from the above area value 3 Molar selectivity of F (monofluoromethane). The results are shown in Table 1.
(example 2)
Will CH 3 OH、SF 6 The flow rates of Ar were changed to 10sccm, 20sccm, and 270sccm, respectively, in the same manner as in example 1. The results are shown in Table 1.
(example 3)
Will CH 3 OH、SF 6 The flow rates of Ar were changed to 10sccm, 30sccm, and 260sccm, respectively, in the same manner as in example 1. The results are shown in Table 1.
(example 4)
Will CH 3 OH、SF 6 The same procedure as in example 1 was repeated, except that the flow rates of Ar were changed to 10sccm, 50sccm, and 240sccm, respectively. The results are shown in Table 1.
(example 5)
Will CH 3 OH、SF 6 The same procedure as in example 1 was repeated, except that the flow rates of Ar were changed to 10sccm, 240sccm, and 50sccm, respectively. The results are shown in Table 1.
(example 6)
Changing the inert gas from Ar to N 2 Otherwise, the same procedure as in example 3 was repeated. The results are shown in Table 1.
(example 7)
Using CH 4 As the compound of formula 1, reacting CH 4 、SF 6 The same procedure as in example 1 was repeated, except that the flow rates of Ar were changed to 10sccm, 30sccm, and 260sccm, respectively. The results are shown in Table 1.
(example 8)
Will CH 4 、SF 6 The same procedure as in example 7 was repeated, except that the flow rates of Ar were changed to 10sccm, 50sccm, and 240sccm, respectively. The results are shown in Table 1.
(example 9)
Changing the inert gas from Ar to N 2 Otherwise, the same procedure as in example 7 was repeated. ResultsShown in table 1.
(example 10)
Using CH 3 OH as the compound of formula 1, CF is used 4 As the fluorine-containing inorganic compound, CH 3 OH、CF 4 The same procedure as in example 1 was repeated, except that the flow rates of Ar were changed to 10sccm, and 280sccm, respectively. The results are shown in Table 1.
(example 11)
Using CH 3 COCH 3 As the compound of formula 1, reacting CH 3 COCH 3 、SF 6 The same procedure as in example 1 was repeated, except that the flow rates of Ar were changed to 10sccm, 50sccm, and 240sccm, respectively. The results are shown in Table 1.
(example 12)
Using CH 3 OCH 3 As the compound of formula 1, reacting CH 3 OCH 3 、SF 6 The flow rates of Ar were changed to 10sccm, 50sccm, and 240sccm, respectively, in the same manner as in example 1. The results are shown in Table 1.
(example 13)
Using CH 3 Cl as a compound of formula 1, reacting CH 3 Cl、SF 6 The same procedure as in example 1 was repeated, except that the flow rates of Ar were changed to 10sccm, 50sccm, and 240sccm, respectively. The results are shown in Table 1.
[ Table 1]
As is clear from Table 1, in the examples, monofluoromethane (CH) could be produced without using a catalyst 3 F) In that respect In particular, it is found that in examples 2 to 13 in which the volume ratio of the fluorine-containing inorganic compound to the compound of formula 1 is 0.8 or more, the by-production of hydrocarbons is sufficiently suppressed. Further, as is clear from comparison with example 1, examples 2 to 5 in which the volume ratio of the fluorine-containing inorganic compound to the compound of formula 1 was 1.8 or more produced monofluoromethane (CH) 3 F) The aspect is advantageous.
Industrial applicability
According to the present invention, monofluoromethane can be produced in a gas phase flow manner without using a catalyst. The production method of the present invention can avoid a decrease in yield due to a decrease in activity of the catalyst, can produce monofluoromethane continuously, and has high industrial applicability.
Claims (6)
1. A process for producing monofluoromethane, which comprises the steps of discharging a raw material gas in a continuously circulating state and then continuously discharging the raw material gas outside the discharge region,
the raw material gas contains a fluorine-containing inorganic compound, formula 1: CH (CH) 3 -R, and an inert gas, in formula 1: CH (CH) 3 R represents a compound wherein R is a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group other than a hydrocarbon group.
2. The method for producing monofluoromethane according to claim 1, wherein the fluorine-containing inorganic compound is selected from SF 4 、SF 6 、SOF 2 、SO 2 F 2 、HF、NF 3 、CF 4 、BF 3 And SiF 4 More than one of them.
3. The method for producing monofluoromethane according to claim 1 or 2, wherein the inert gas is selected from N 2 And Ar.
4. The method for producing monofluoromethane according to any one of claims 1 to 3, wherein the total content of the fluorine-containing inorganic compound and the compound represented by formula 1 in the raw material gas is 1% by volume or more and 85% by volume or less.
5. The method for producing monofluoromethane according to any one of claims 1 to 4, wherein the volume ratio of the fluorine-containing inorganic compound to the compound represented by formula 1 is 0.8 or more.
6. The method for producing monofluoromethane according to any one of claims 1 to 5, wherein the volume ratio of the fluorine-containing inorganic compound to the compound represented by formula 1 is 1.8 or more.
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| PCT/JP2021/019064 WO2021241371A1 (en) | 2020-05-29 | 2021-05-19 | Method for producing monofluoromethane |
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| US (1) | US20230159415A1 (en) |
| EP (1) | EP4159707A1 (en) |
| JP (1) | JPWO2021241371A1 (en) |
| KR (1) | KR20230017769A (en) |
| CN (1) | CN115485256A (en) |
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| CN115838320A (en) * | 2023-02-28 | 2023-03-24 | 山东东岳化工有限公司 | Method for preparing monofluoromethane |
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| WO2023182304A1 (en) * | 2022-03-24 | 2023-09-28 | 日本ゼオン株式会社 | Method for producing fluorohydrocarbon |
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| JP2001054721A (en) * | 1999-06-04 | 2001-02-27 | Kashiyama Kogyo Kk | Method and device for decomposing fluorocarbons |
| JP5013692B2 (en) | 2004-09-16 | 2012-08-29 | 昭和電工株式会社 | Fluoromethane production method and product |
| JP2013006786A (en) * | 2011-06-23 | 2013-01-10 | Nippon Zeon Co Ltd | Method for producing fluorinated alkane |
| JP6578993B2 (en) * | 2016-03-02 | 2019-09-25 | 日本ゼオン株式会社 | Method for producing fluorinated hydrocarbon |
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2021
- 2021-05-19 KR KR1020227039964A patent/KR20230017769A/en unknown
- 2021-05-19 CN CN202180031838.5A patent/CN115485256A/en active Pending
- 2021-05-19 JP JP2022526939A patent/JPWO2021241371A1/ja active Pending
- 2021-05-19 WO PCT/JP2021/019064 patent/WO2021241371A1/en unknown
- 2021-05-19 US US17/997,262 patent/US20230159415A1/en active Pending
- 2021-05-19 EP EP21812400.6A patent/EP4159707A1/en active Pending
- 2021-05-21 TW TW110118482A patent/TW202206403A/en unknown
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| US3840445A (en) * | 1972-05-15 | 1974-10-08 | Phillips Petroleum Co | Two-stage electrochemical octafluoropropane production |
| CN1106077A (en) * | 1993-08-31 | 1995-08-02 | 美国3M公司 | Process for preparating fluorochemicals |
| CN1398248A (en) * | 2000-02-10 | 2003-02-19 | 南非核能源有限公司 | Treatment of fluorocarbon feedstocks |
| JP2008201723A (en) * | 2007-02-20 | 2008-09-04 | Fuji Xerox Co Ltd | Microfluid device, reaction unit, and reaction method |
| US20140343245A1 (en) * | 2011-09-14 | 2014-11-20 | Pacifitech Pty Ltd | Plasma Treatment of Halogenated Compounds |
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| CN115838320A (en) * | 2023-02-28 | 2023-03-24 | 山东东岳化工有限公司 | Method for preparing monofluoromethane |
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| WO2021241371A1 (en) | 2021-12-02 |
| EP4159707A1 (en) | 2023-04-05 |
| US20230159415A1 (en) | 2023-05-25 |
| KR20230017769A (en) | 2023-02-06 |
| TW202206403A (en) | 2022-02-16 |
| JPWO2021241371A1 (en) | 2021-12-02 |
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